N-fluoropyridinium salt and process for preparing same

ABSTRACT

A pyridine-compound is reacted with fluorine together with a .[.Bronsted.]. .Iadd.Bronsted .Iaddend.acid-compound or Lewis acid to form a N-fluoropyridinium salt which is very active to other compounds but is very selective for the preparation of a desired product and this product is very useful for a fluorine-introducing agent which makes it useful for the preparation of fluoro-compounds such as thyroid inhibitor.

.[.This application is a continuation of application Ser. No. 022,275,filed Mar. 5, 1987, now abandoned, which was a continuation-in-partapplication of Ser. No. 870,010, filed Jun. 3, 1986, nowabandoned..]..Iadd.

CROSS REFERENCE

This application is a Re-issue of Ser. No. 07/296,411 filed Jan. 09,1989, U.S. Pat. No. 4,996,320, which is a Continuation of Ser. No.07/022,275 filed Mar. 05, 1987, (abandoned), which is aContinuation-in-part of Ser. No. 06/870,010 filed Jun. 03, 1986(abandoned). .Iaddend.

BACKGROUND OF THE INVENTION

The present invention relates to a N-fluoropyridinium salt and a processfor preparing same. The N-fluoropyridinium salts according to thepresent invention are very useful as a fluorine atom introducing agentas seen from the examples 66-133 hereinafter illustrated. The saltsaccording to the invention have a widespread use because of their highreactivity with a wide variety of compounds and selectivity for anydesired products. For example, said salt can be used for the preparationof 3-fluoro-4-hydroxyphenlacetic acid which is useful as a thyroidinhibitor by reacting the former with p-hydroxyphenylacetate followed bya common hydrolysis reaction as illustrated in examples 79 to 82referred to hereinafter.

Heretofore, it has been well known in the art that fluorine compoundsare significantly distinguished from chlorine compounds, brominecompounds, and iodine compounds in their physical properties andreactivities, because fluorine atom have characteristics such as veryhigh electronegativity, high ionization energy, extremely high bondingability with other atoms, small Van der Waals diameter, lack of ad-electron orbit and the like (N. Ishikawa & Y. Kobayashi; FLUORINECOMPOUNDS; THEIR CHEMISTRY AND APPLICATIONS; KodanshaSchientific, pp.69-70. 1979). Therefore, fluorination reactions naturally havesignificantly different aspects from other halogenation reactions suchas chlorinations, brominations and iodinations.

In reactions with organic compounds, fluorine, contrary to chlorine,bromine and iodine, reacts very violently, readily giving rise to thefission of the C--C bond of organic compounds and in cases where thereaction is excessively violent, fire or explosion in turn can breakout. The abnormality of fluorination reactions relative to otherhalogenation reactions may be readily understood from the comparison ofheat of formation in halogenation reactions (see the description onpages 69-75 of the above article) as follows:

    ______________________________________                                                      ΔH (Kcal/mol)                                             type of reaction                                                                              X = F   Cl       Br   I                                       ______________________________________                                        C═C + X.sub.2 --CX--CX                                                                    -111    -36      -23  -16                                     C--H + X.sub.2 --C--X + HX                                                                    -105    -25       -9   +6                                     ______________________________________                                    

As seen from the above Table, since the heat of reaction in thefluorination reactions amount to ever 100Kcal/-mol, while the bondingenergy between carbon-carbon atoms is approximately only 60Kcal/mol, thecontrol of fluorination reactions is very difficult, contrary to otherhalogenation reactions. Accordingly, the development of fluorinationreactions having better selectivity has been an important subject matterin fluorination industries.

For the purpose resolving the above problem, a wide variety ofcompoounds for introducing fluorine atoms have heretofore been studiedand developed. As such compounds, for example,trifluoromethyl-hypofluorite (CF₃ OF), trifluoroacetyl-hypofluorite (CF₃COOF), acetyihypofluorite (CH₃ COOF), xenon difluoride XeF₂), FClO₃,sulfur tetrafluoride (SF₄), die-thylaminosulfur trifluoride (ET₂ NSF₃),CClHFCF₂ NEt₂,CF₃ CFHCF₂ NEt₂, heavy metal fluorides such as AgF, HgF,CoF₃,AgF₂ and the like were known in the art (see pages 79-94 of theabove-mentioned article). However, these compounds have drawbacks suchas poor selectivity for the desired reaction, are highly hazardous tohandle, have high cost, unstableness, a limited scope of application,and the like which make them commercially unsatisfactory. On the otherhand, hydrogen fluoride, hydrofluoric acid, potassium fluoride, cesiumfluoride, and the like which are known as inexpensive agents forintroducing fluorine atoms are inferior in electrophilic reactivity,which imposes such limitations that they cannot perform electrophilicsubstitutions for aromatic nuclei or negatively charged carbon ions.These compounds also present serious problems in handling becausehydrogen fluoride or hydrofluoric acid, for example, are highly toxic.It has been suggested that a pyridine. F₂ complex can be used as afluorine atom-introducing agent, but it can only offer low total yieldof fluorination reactions [see, Z. Chem., 12, 292 (1972)] and moreover,said complex is highly hygroscopic and thermally unstable so thatexplosions may break out at above -2°C. [Z. Chem., 5, 64 (1965)]. Fromthe above, it can hardly be said that the complex is a usefulfluorinating agent. Recently, N-fluoro-N-alkylarenesulfoneamide havebeen reported as fluorine atom-introducing agents, but these compoundsare low in reactivity and only effective for particular reaction species(negatively charged carbon ions) [J. Amer. Chem. Soc. 106, 452 (1984)].Therefore, a strong need exists for the development of highlysatisfactory fluorine atom-introducing agents.

As a result of a series of earnest investigations by the presentinventors towards the development of a novel fluorine-introducing agent,they have succeeded in developing a novel fluorine-introducing agentwhich is active but stable allowing the easy handling of the agent whichstill retains high selectivity of a desired reaction, thus completingthe present invention. The compounds according to the present inventionhave high reactivity with a variety of compounds and high selectivityfor any desired compounds, which allows the compounds to be very usefulfor the synthesis of a variety of fluorine-containing compounds in ashortened process. For example, a thyroid inhibitor,3-fluoro4-hydroxy-phenylacetic acid could easily be prepared fromp-hydorxyphenylacetate available industrially (see, Examples 79-82hereinafter described).

SUMMARY OF THE INVENTION

The present invention relates to a N-fluoropyridiuium salt representedby the formula: ##STR1## wherein R¹, R², R³, R⁴ and R⁵ represent ahydrogen atom, a halogen atom, an alkyl, aryl, acyl, alkoxycarbonyl,aryloxycarbonyl, carbamoyl, nitro, cyano, alkylsulfonyl arylsulfonyl,hydroxy, alkoxy, aryloxy, acyloxy, acylthio, amido, alkanesulfonyloxy,or arenesulfonyloxy group; X.sub.⊖ represents a conjugate base ofBronsted acid except for F.sub.⊖, Cl.sub.⊖, Br.sub.⊖ and I.sub.⊖ whichare conjugate bases of hydrogen halides; and R¹, R², R³, R⁴ and R⁵ maybe combined together directly or through a hetero atom or atoms in avariety of combinations to form a cyclic structure, while X.sub.⊖ may becombined directly or through a hertro-atom or atoms with R¹, R², R³, R⁴and R⁵ in various combinations.

The present invention further relates to a process for producing theabove N-fluoropyridinium salt by reacting a pyridine-compound having thegeneral formula: ##STR2## wherein R¹ to R⁵ represent the same meaning asdefined above, with fluorine (F₂) and a Bronsted acid compound havingthe general formula:

    XM                                                         (III)

wherein M represents a hydrogen atom, a metal atom, an ammonium residue,a pyridinium residue or a group SiR⁶ R⁷ R⁸ in which R⁶,R⁷ and R⁸ are anaklyl, aryl, alkoxy, aryloxy, acyloxy group, or a halogen atom; and Xrepresents the same meaning as above.

DETAILED DESCRIPTION OF THE INVENTION

The pyridine-copmpounds set forth in formula (II) employable in thepresent invention are those which are easily available or which may beprepared readily and are exemplified by pyridine; straight or branchedalkylated or cyclic alkylated pyridine such as methyipyridine,dimethylpyridine, trimethylpyridine, tetramethylpyridine,pentamethylpyridine, ethylpyridine, diethylpyridine, butylpyridine,dibutylpyridine, tributylpyridine, pentylpyridine, hexylpyridine,decylpyridine, (trifluoromethyl)-pyridine, bis(trifluoromethyl)pyridinetris(trifluoromethyl)-pyridine, (trichloromethyl)pyridine,(pentafluoroethyl)-pyridine, (perfluorooctyl)pyridine,(methoxymethyl)pyridine, ethyl pyridylacetate, pyridylacetonitrile,pyridylacetone, and the like; halopyridines such as chloropyridine,bromopyridine, fluoropyridine, dichloropyridine, difluoropyridine,trichloropyridine, tetrachloropyridine, pentachloropyridine,trifluoropyridine, pentafluoropyridine, chlorofluoropyridine,dichlorofluoropyridine, and so on; (trifluoromethyl)chloropyridine,(trifluoromethyl)dichloropyridine, (trifluoromethyl)trichloropyridine,(trifluoromethyl)fluoropyridine, methylchloropyridine, phenylpyridine,diphenylpyridine, triphenylpyridine,-dipyridyl, acetylpyridine,bisacetylpyridine, benzoylpyridine;(alkoxycarbonyl)pyridine or(aryloxycarbonyl)pyridine such as(methoxycarbonyl)-pyridine,(exthoxycarbonyl)pyridine,(butoxycarbonyl)pyridine,bis(ethoyxcarbonyl)pyridine,bis(trifluoroethoxycarbonyl)-pyridine,tris(methoxycarbonyl)pyridine,(-phenoxycarbonyl)-pryidine;2,3-pryidinedicarboxylic anhydride,nitropyridine, cyanopyridine,dicyanopyridine, tricyanopyridine, benzenesulfonylpyridine,methylsulfonylpyridine, chlorocyanopyridine, formylpyridine,(haloformyl)pyridine, nicotinamide,picolinamide,(dimethylaminocarbonyl)pyridine, methoxypyridine, dimethoxypyridine,propoxypyridine, butoxypyridine, menthoxypyridine,trifluoromethoxypyridine, acetoxypridine, trifluoroacetoxypyridine,phenoxypyridine, acetylthipoyridine, methanesulfonyloxypyridine,benzenesulfonyloxypyridine, acetylaminopyridine,3-hydroxypyridine, and1,2,3,4,5,6,7,8-octahydroacridine.

As the .[.Brosted.]. .Iadd.Bronsted .Iaddend.acid-compounds representedby the formula (III), there may be mentioned the following compounds:sulfonic acids or sulfuric acids such as methanesulfonic acid,butanesulfonic acid, benzensulfonic acid, toluenesulfonic acid,nitrobenzensulfonic acid, dinitrobenzensulfonic acid,trinitrobenzensulfonic acid, trifluoromethanesulfonic acid,perfluorobutanesulfonic acid, perfluorooctanesulfonic acid,trichloromethanesulfonic acid, diflurormethanesulfonic acid,trifluoroethanesulfonic acid, fluorosulfonic acid, chlorosulfonic acid,monomethylsulfric acid, sulfuric acid, camphorsulfonic acid,bromocamphorsulfonic acid, Δ⁴ -cholestene-3-on-6-sulfonic acid,1-hydroxy- p-methane-2-sulfonic acid, p-styrenesulfonic acid,β-styrenesulfonic acid, poly(p-styrenesulfonic acid), vinyl-sulfonicpoly(vinylsulfonic acid), poly(2-acrylamide-2-methyl-1-propanesulfonicacid), and a copolymer of said propanesulfonic acid with styrene,perfluoro-3,5-dioxa-4-methyl-7-octenesulfonic acid,poly(-perfluoro-3,6-dioxa-4-methyl-7-octensulfonic acid) and a copolymerof said octnesulfonic acid with tetrafluoroethylene, and the like;phosphoric acid; nitric acid; halogen acids such as perchloric acid,perbromic acid, periodic acid, chloric acid, bromic acid, and the like;carboxylic acids such as acetic acid, formic acid, trichloro-aceticacid, trifluoroacetic acid, pentafluoropropionic acid, dichloroaceticacid, acrylic acid, poly(acrylic acid),poly-(perfluoro-3,6-dioxa-4-methyl-7-octenoic acid) and a copolymer ofsaid octenoic acid with tetrafluoroethylene and so on; compoundsresulting from hydrogen halide and Lewis acids such as HBF₄, HPF₆,HSbF₄, HSbF₆, HAsF₆, HBCl₃ F, HSiF₅ and the like; metal salts of theabove mentioned .[.Brosted.]. .Iadd.Bronsted .Iaddend.acids; a varietyof ammonium salts or pryidinium salts of the above mentioned.[.Brosted.]. .Iadd.Bronsted .Iaddend.acids; silyl compounds resultingfrom the substitution of hydrogen atom or atoms of the above mentioned.[.Brosted.]. .Iadd.Bronsted .Iaddend.acids with a group SiR⁶ R⁷ R⁸wherein R⁶, R⁷ and R⁸ are the same as defined above, or metal bifluoridesuch as sodium bifluoride, for example. As the group SiR⁶ R⁷ R⁸, theremay be listed, for example, trimethylsilyl, triethylsilyl,dimethylbutylsilyl, dimethylphenylsilyl, triphenylsilyl, trihalosilyl,triacetylsilyl, triacetoxysilyl, trimethoxysilyl, triphenoxysilyl. Asthe metals for the metal salts of Brosted acids reference is preferablymade to alkali metals or alkaline earth metals from the aspect ofeconomy and reaction efficiency. Further, as the variety of ammoniumsalts or pyridinium salts, there may be mentioned ammonium salts,trimethylammonium salts, triethylammonium salts, tetraethylammoniumsalts, benzyltrimethylammonium salts, phenylammonium salts,dimethylphenylammonium salts, naphthaylammonium salts, pryidinium salts,dimethylpyridinium salts, trimethylpyridinium salts, quinolinium saltsand the like.

Of the N-fluoropyridinium salts represented by formula (I), in the casewhere X.sub.⊖ and R¹, R², R³, R⁴ and R⁵ are combined together in avariety combinations, the pyridinium compounds represented by formula(II) as the raw material include, for example, sodium pyridinesulfonate,pyridinesulfonic acid, ammonium pyridinesulfonate, potassiumpyridylethylsulfonate, sodium pyridinecarboxylate and the like.

The pyridine.F₂ complex where X.sub.⊖ represents F.sub.⊖ which is theconjugatge base of hydrogen halide in the N-fluoropyridinium salts has aserious drawback in that it is unstable and explodes at a temperatureabove -2° C. and when the conjugate base is Cl.sub.⊖, Br.sub.⊖ orI.sub.⊖ the corresponding N-fluoropyridinium salts are difficult insynthesis.

The Brosted acid-compounds for achieving better reaction efficienciesshould be equal to or in excess molar amount to that of the hostmaterial, but preferably should be an equi-molar amount from an economicviewpoint. Fluorine employed in the present invention should preferablybe diluted with 50 to 99.9% by volume of an inert gas in order tosuppress any violent reactions. The diluting gas includes, by way ofexample, nitrogen, helium, argon, tetrafluoromelthane, sulfurhexafluoride and the like.

The fluorine gas for achieving better reaction efficiencies should beused in an equi-molar or in excess molar amount to be the host material.However since the amount may vary depending upon the manner ofintroduction, reaction temperature, reaction solvent, reaction apparatusand so on, it may preferably be selected in amounts required foreliminating the last traces of the host material.

The reaction is preferably carried out by the sue of a solvent. As thesolvent, acetonitrile, methylene chloride, chloroform, carbontetrachloride, trichlorofluoromethane, trichlorotrifluoroethane, ethylacetate, diethyl ether, tetrahydrofuran, and the like or a mixturethereof may be used.

A reaction temperature of -100° to +40° C. may be selected, but therange of temperature of from -90° C. to room temperature is beingpreferred for better reaction yields.

In carrying out the process of the present invention it is occasionallypreferable for improving the reaction efficiency to employ a trappingagent such as sodium fluoride to capture hydrogen fluoride produced as aby-product.

Of the N-fluoropyridinium salts having the formula (I),N-fluoropryidinium salt having the formula ##STR3## (wherein R¹ to F⁵have the same meaning as above and Y represents a Lewis acid), can beprepared by reacting the pyridine-compound represented by formula (II)with fluorine (F₂) and a Lewis acid having the formula

    Y                                                          (IV)

The Lewis acid, the starting material set forth in formula (IV), mayinclude, for example, boron trifluoride, boron trichloride,triacetoxyboron, tri(tgrifluoroacetoxy)boron, aluminum trifluoride,aluminum trichloride, aluminum tribromide, phosphorous trifluoride,phosphorous pentafluoride, phosphorus pentachloride, arsenictrifluoride, arsenic trichloride, arsenic pentafluoride antimonytrifluoride, antimony pentafluoride, antimony dichlorotrifluoride,silicon tetrafluoride, trimethylfluorosilane,dimethylphenylfluorosilane, sulfur trioxide, titanium tetrachloride,stannic chloride, ferric chloride, and iodine pentafluoride. Etherealcomplexes of these Lewis acids may also employed without any problems.These Lewis acids may be employed in an equi-molar or in excess molaramount to he host material (II) for achieving a better reactionefficiency, but from the standpoint of economy the equi-molar amount bepreferable. The manner in which fluroine is used and the amount offluorine to be used are similar to the above embodiment.

A reaction of the present invention is preferably carried out by using areaction solvent. The reaction solvent may include, for example,acetonitrile, methylenechloride, chloroform, trichlorofluoromethane,trichlorofluoroethane, ethylacetate, diethylether, tetrahydrofuran or amixture thereof.

A reaction temperature may generally be in the range of .[.-100+'° C.,.]. .Iadd.-100° to +40° C. .Iaddend.and preferably a range of .[.-90+°C. .]. .Iadd.-90° to +20° C. .Iaddend.may be selected for a betteryield.

The compounds (I) according to the present invention can be readilyprepared and are in most cases stable in air at room temperature. Thesecompounds enable the simple and selective introduction of a fluorineatom to a comtemplated compound with good efficiency and therefore serveas a superior fluorine-introducing agent. Further, the compoundsaccording to the present invention, after they have once been reacted,reproduce the pyridine-compounds or form protonic salts of silyl saltsof pyridine-compounds which can readily generate the startingpyridine-compounds by neutralization or treatment with water.

The following examples will illustrate the present invention in moredetail.

EXAMPLE 1 Preparation of N-fluoropyridiniumtrifluoromethanesulfonate##STR4##

To a 50 ml trichlorofluoromethane solution containing 1.0 g (12.6 mmoles) of pyridine a mixed gas of fluorine and nitrogen in a volumetricratio of 1:9 was introduced at a rate of 30 ml/min. at -78° C. undervigorous stirring. The amount of the fluorine gas introduced amounted to34.8 mmoles. Subsequent to the fluorine introduction, 20 ml of anhydrousacetonitrile and 2.2 g (12.8 mmoles) of sodiumtrifluoro-methanesulfonate as a XM reactant were added to the reactionsolution after which the temperature of the solution was raised to -40°C., while removing the solvent with the aid of an aspirator. Thesolvent, after filtering sodium fluoride formed as a byproduct, wasdistilled off and the resultant residue was recrystallized from THF togive 1.75 g (yield: 67%) of N-fluoropyridiniumtrifluoromethanesulfonate, the physical properties of which are shown inTable 6.

EXAMPLE 2 Preparation of N-fluoropyridiniumtrifluoromethanesulfonate##STR5##

To a 100 ml anhydrous acetonitrile solution containing 10 g (0.126 mole)of pyridine a mixed gas of fluorine and nitrogen was introduced at arate of 90 ml/min. at -4020 C. under virorous stirring. The amount ofthe flourine gas introduced amounted to 0.18 mole. Subsequent to thefluorine introduction, 22 g (0.128 mole) of sodiumtrifluoromethanesulfonate as a XM reactant was added to the reactionsolution after which the resultant reaction solution was maintained at-40° C. for 5 hours under stirring. Subsequently, the solvent, afterfiltering sodium fluoride, was distilled off and the resultant residuewas recrystallized from methylene chloride to give 17.5 g (yield: 71%)of N-fluoropyridinium trifluoromethanesulfonate. The product thusobtained was repurified with methylene chloride/acetonitrile to recover13.8 g (yield: 56%).

EXAMPLES 3-15

Example 3 was carried out as in Example 1 and Examples 4-15 were carriedout as in Example 2. The reactants used and the results obtained areshown in Table 1 and the physical properties of the products are shownin Table 6.

Further, Example 12 employed sodium D-camphorsulfonate as the XMreactant and the angle of specific rotatory power of the product was[α]_(D) ²² =+29.51 (c=0.664, CH₃ CN).

                                      TABLE 1                                     __________________________________________________________________________         pyridine-                                             yield              Example                                                                            compound        XM            product                 (%)                __________________________________________________________________________          ##STR6##       CF.sub.3 SO.sub.3 Na                                                                         ##STR7##               60                 4                                                                                   ##STR8##       NaPF.sub.6                                                                                   ##STR9##               34                 5                                                                                   ##STR10##      NaSbF.sub.6                                                                                  ##STR11##              51                 6                                                                                   ##STR12##      NaClO.sub.4                                                                                  ##STR13##              72                 7                                                                                   ##STR14##      CF.sub.3 SO.sub.3 H                                                                          ##STR15##              44                 8                                                                                   ##STR16##      CF.sub.3 SO.sub.3 SiMe.sub.3                                                                 ##STR17##              45                 9                                                                                   ##STR18##      CF.sub.3 SO.sub.3 H                                                                          ##STR19##              41                 10                                                                                  ##STR20##      CF.sub.3 SO.sub.3 SiMe.sub.3                                                                 ##STR21##              62                 11                                                                                  ##STR22##      FSO.sub.3 H                                                                                  ##STR23##              49                 12                                                                                  ##STR24##                                                                                     ##STR25##                                                                                   ##STR26##              50                 13                                                                                  ##STR27##      FSO.sub.3 H                                                                                  ##STR28##              56                 14                                                                                  ##STR29##      CF.sub.3 COOSiMe.sub.3                                                                       ##STR30##              77                 15                                                                                  ##STR31##      CF.sub.3 SO.sub.3 H                                                                          ##STR32##              60                 __________________________________________________________________________

EXAMPLE 16 ##STR33##

In 20 ml of anhydrous acetonitrile 0.50 g (4.67 mmoles) of 2.6-dimethylpyridine and 0.803 g (4.67 mmoles) of sodiumtrifluoromethanesulfonate as the XM reactant were dissolved, and to theresultant solution a mixed gas of fluorine and nitrogen (1:9) was addedat a rate of 30 ml/min. at -40° C. under vigorous stirring. The amountof the fluorine gas introduced amounted to 8.93 mmoles. After thecompletion of the reaction, sodium fluoride was filtered and the solventwas distilled off. The resultant residue was recrystallized from THF togive 0.88 g (yield: 73%) of N-fluoro-2,6-diemthyl-pyridiniumtrifluoromethanesulfonate. The resultant product was furtherrecrystallized with THF/acetonitrile to obtain 0.82 g (yield: 69%), thephysical properties of which are shown in Table 6.

EXAMPLES 17-26

Examples 17-26 were carried out as in Example 16 and the results areshown in Table 2 with the physical properties in Table 6. In Example 22,2 -1-menthoxypyridine [[α]D²⁰ =-110.7 (c=0.994, CHCl₃)] was used as thepyridine compound for the starting material and the specific rotarypower of the resultant N-fluoro-2-1-menthoxypyridiniumtrifluoromethanesulfonate was [α]D²⁵ =-77.73 (c=4.16, CHCl₃).

                                      TABLE 2                                     __________________________________________________________________________         Pyridine-                                 Yield                          Example                                                                            Compound         XM     Product           (%)                            __________________________________________________________________________    17                                                                                  ##STR34##       CF.sub.3 SO.sub.3 Na                                                                  ##STR35##        82                             18                                                                                  ##STR36##       CF.sub.3 SO.sub.3 Na                                                                  ##STR37##        72                             19                                                                                  ##STR38##       n-C.sub.4 F.sub.9 SO.sub.3 Na                                                         ##STR39##        87                             20                                                                                  ##STR40##       CF.sub. 3 SO.sub.3 Na                                                                 ##STR41##        60                             21                                                                                  ##STR42##       CF.sub.3 SO.sub.3 Na                                                                  ##STR43##        73                             22                                                                                  ##STR44##       CF.sub.3 SO.sub.3 Na                                                                  ##STR45##        57                             23                                                                                  ##STR46##       CF.sub.3 SO.sub.3 Na                                                                  ##STR47##        90                             24                                                                                  ##STR48##       CF.sub.3 SO.sub.3 Na                                                                  ##STR49##        19                             25                                                                                  ##STR50##       CF.sub.3 SO.sub.3 H                                                                   ##STR51##        75                             26                                                                                  ##STR52##       CF.sub.3 SO.sub.3 Na                                                                  ##STR53##        60                             Example 27                                                                     ##STR54##                                                                

To a 5 ml anhydrous acetonitrile solution containing 0.408 g (5.17mmoles) of pyridine, 1.0 ml (5.17 mmoles) of trimethylsilyltrifluoromethanesulfonate as the XM reactant was added at -40° C. understirring. To the resultant solution a mixed gas of fluorine and nitrogen(1:9), 10 minutes after the addition, was introduced at a rate of 15ml/min. The amount of fluorine gas introduced was 15.5 mmoles. After thecompletion of the reaction, an amount of ether cooled to -60° C. wasadded to the solution to precipitate crystals which were filtered togive 0.99 g (yield: 78%) of N-fluoropyridiniumtrifluoromethanesulfonate.

EXAMPLES 28-38

Examples 28-38 were carried out as in Example 27 except that in Examples34 the gas ratio of fluorine:nitrogen was 2.5:97.5. The results aresummarized in Table 3 with the physical properties in Table 6.

                                      TABLE 3                                     __________________________________________________________________________         Pyridine-                                  Yield                         Example                                                                            Compound         XM       Product          (%)                           __________________________________________________________________________    28                                                                                  ##STR55##       CH.sub.3 SO.sub.3 SiMe.sub.3                                                            ##STR56##       42                            29                                                                                  ##STR57##       CF.sub.3 SO.sub.3 SiMe.sub.3                                                            ##STR58##       55                            30                                                                                  ##STR59##       CF.sub.3 SO.sub.3 SiMe.sub.3                                                            ##STR60##       79                            31                                                                                  ##STR61##       CF.sub.3 SO.sub.3 SiMe.sub.3                                                            ##STR62##       71                            32                                                                                  ##STR63##       CF.sub.3 SO.sub.3 SiMe.sub.3                                                            ##STR64##       69                            33                                                                                  ##STR65##       CF.sub.3 SO.sub.3 SiMe.sub.2 Ph                                                         ##STR66##       71                            34                                                                                  ##STR67##       CF.sub.3 SO.sub.3 SiMe.sub.3                                                            ##STR68##       68                            35                                                                                  ##STR69##       CF.sub.3 SO.sub.3 SiMe.sub.3                                                            ##STR70##        30                           36                                                                                  ##STR71##       CF.sub.3 SO.sub.3 SiMe.sub.3                                                            ##STR72##       28                            37                                                                                  ##STR73##       CF.sub.3 SO.sub.3 SiMe.sub.3                                                            ##STR74##       52                            38                                                                                  ##STR75##       CF.sub.3 SO.sub.3 SiMe.sub.3                                                            ##STR76##       86                            __________________________________________________________________________

.Iadd.EXAMPLE 39 .Iaddend. ##STR77##

In a 25 ml pear-shaped flask, 2,4,6-trimethylpyridine (1.21 g, 10mmoles), sodium borofluoride (1.23 g 10 mmoles) as the XM reactant andanhydrous sodium fluoride (2.1 g, 50 mmoles) were dissolved in 15 ml ofanhydrous acetonitrile and to the resulting solution a mixed gas ofnitrogen/fluorine (9:1) was introduced at a rate of 50 ml/min. at -40 °C. under vigorous stirring.

The amount of fluorine introduced was 20 mmoles. After the completion ofthe reaction, precipitates were filtered and then the solvent wasdistilled off. The resultant residue was recrystallized fromacetonitrile/diethylether to obtain 1.59 g (yield: 70%)ofN-fluoro-2,4,6-trimethylpyridinium tetrafluoroborate the physicalproperties of which are shown in Table 6.

EXAMPLE 40 ##STR78##

This example was effected as in example 39 to giveN-fluoro-4-methylpyridinium trifluoromethanesulfonate in 90% yield, thephysical properties of which are indicated in Table 6.

EXAMPLE 41-60

Further examples were carried out by using various pyridine compoundsand XM. The experimental methods, the reaction products and the yeildsare shown in Table 4. The physical properties of the products areindicated in Table 6.

                                      TABLE 4                                     __________________________________________________________________________    Ex-                                Ex-                                        am- Pyridine                  Trapping                                                                           perimental              Yield              ple Compound          XM      Agent                                                                              Method                                                                              Product           (%)                __________________________________________________________________________    41                                                                                 ##STR79##        CF.sub.3 SO.sub.3 Na                                                                  --   Ex. 16                                                                               ##STR80##        76                 42                                                                                 ##STR81##        CF.sub.3 SO.sub.3 Na                                                                  NaF  Ex. 39                                                                               ##STR82##        86                 43                                                                                 ##STR83##        NaBF.sub.4                                                                            NaF  Ex. 39                                                                               ##STR84##        65                 44                                                                                 ##STR85##        CF.sub.3 SO.sub.3 Na                                                                  NaF  Ex. 39                                                                               ##STR86##        26                 45                                                                                 ##STR87##        NaClO.sub.4                                                                           --   Ex. 39                                                                               ##STR88##        81                 46                                                                                 ##STR89##        CF.sub.3 SO.sub.3 SiMe.sub.3                                                          --   Ex. 27                                                                               ##STR90##        60                 47                                                                                 ##STR91##        CF.sub.3 SO.sub.3 Na                                                                  NaF  Ex. 39                                                                               ##STR92##        87                 48                                                                                 ##STR93##        CF.sub.3 SO.sub.3 Na                                                                  NaF  Ex. 39                                                                               ##STR94##        62                 49                                                                                 ##STR95##        CF.sub.3 SO.sub.3 Na                                                                  --   Ex. 16                                                                               ##STR96##        72                 50                                                                                 ##STR97##        CF.sub.3 SO.sub.3 Na                                                                  NaF  Ex. 39                                                                               ##STR98##         33                51                                                                                 ##STR99##        CF.sub.3 SO.sub.3 SiMe.sub.3                                                          NaF  Ex. 39                                                                               ##STR100##       18                 52                                                                                 ##STR101##       CF.sub.3 SO.sub.3 SiMe.sub.3                                                          --   Ex. 2                                                                                ##STR102##       15                 53                                                                                 ##STR103##       CF.sub.3 SO.sub.3 Na                                                                  NaF  Ex. 39                                                                               ##STR104##       1.3                54                                                                                 ##STR105##       CF.sub.3 SO.sub.3 SiMe.sub.3                                                          --   Ex. 1                                                                                ##STR106##       little             55                                                                                 ##STR107##       CF.sub.3 SO.sub.3 SiMe.sub.3                                                          --   Ex. 1                                                                                ##STR108##       little             56                                                                                 ##STR109##       CF.sub.3 SO.sub.3 SiMe.sub.3                                                          --   Ex. 27                                                                               ##STR110##       68                 57                                                                                 ##STR111##       CF.sub.3 SO.sub.3 Na                                                                  NaF  Ex. 39                                                                               ##STR112##       84                 58                                                                                 ##STR113##       CF.sub.3 SO.sub.3 Na                                                                  NaF  Ex. 39                                                                               ##STR114##       56                  59*                                                                               ##STR115##       CF.sub.3 SO.sub.3 Na                                                                  Na.sub.2 CO.sub.3                                                                  Ex. 39                                                                               ##STR116##       10                 60                                                                                 ##STR117##       CF.sub.3 SO.sub.3 SiMe.sub.3                                                          --   Ex. 1                                                                                ##STR118##       little             __________________________________________________________________________     *Acetonitrile-water (1:1) is used as a reaction medium.                  

EXAMPLE 61 ##STR119##

To a 30 ml anhydrous acetonitrile solution containing 0.71 g (8.98mmole) of pyridine a mixed gas of fluorine and nitrogen (1:9) wasintroduced at a rate of 20 ml/min. at -40° C. under vigorous stirring,the amount of fluorine gas introduced being 26 mmoles. Subsequently, atthe same temperature, 1 ml (8.13 mmole) of an ethereal complex of borontrifluoride as the Lewis acid was added and the resulting solution wasstirred for 5 hours. The post treatment was effected as in example 13 togive 0.91 g (yield: 69%) of N-fluoropyridinium tetrafluoroborate, thephysical properties of which are reproduced in Table 6.

EXAMPLES 62-64

These Examples 62 to 64 were carried out as in Example 61, and theresults of which are summarized in Table 5 with the physical propertiesin Table 6. It should be noted that the appropriate amount of boronfluoride, BF₃, was introduced in the form of a gas, because .[.BD.]..Iadd.BF₃ .Iaddend.is a gas, while SbF₅ and SO₃ are introduced in liquidform.

                                      TABLE 5                                     __________________________________________________________________________    Example                                                                            Pyridine-   Lewis             Yield                                      No.  Compound    Acid                                                                              Product       (%)                                        __________________________________________________________________________    62                                                                                  ##STR120## BF.sub.3                                                                           ##STR121##   62                                         63                                                                                  ##STR122## SbF.sub.5                                                                          ##STR123##   37                                         64                                                                                  ##STR124## SO.sub.3                                                                           ##STR125##   46                                         Example 65                                                                     ##STR126##                                                                   This Example was carried out as in Example 16 except that boron               trifluoride etherate was used in place of sodium trifluoromethanesulfonate     to obtain N-fluoro- 3,5-dichloropyridinium tetrafluoroborate (yield:         79%), the physical properties of which are given in Table 6.              

    TABLE 6                                                                       __________________________________________________________________________    Physical Properties of N-fluoropyridinium Salts                                                                          Elemental analysis                                  F-NMR (ppm)               (Calculated)                       Example No.                                                                          Melting Point (°C.)                                                              (CFCl.sub.3 internal standard in CD.sub.3 CN)                                                   Mass (m/e)                                                                            C % H % N %                        __________________________________________________________________________    1, 2, 7, 8, 27                                                                       185-187   -48.75 (1F, bs, NF)                                                                             227(M.sup.+ -HF)                                                                      29.17                                                                             1.99                                                                              5.66                                        77.61 (3F, s, CF.sub.3)   (29.16)                                                                           (2.04)                                                                            (5.67)                     3      41-42     -46.89 (1F, bs, NF)                                                                             255(M.sup.+ -H)                                                                       34.72                                                                             3.35                                                                              5.07                                        77.75 (3F, s, CF.sub.3)   (34.91)                                                                           (3.30)                                                                            (5.09)                     4       202      -48.58 (1F, bs, NF)                                                                             174, 172                                                                              24.84                                                                             2.10                                                                              5.65                              (decomposition)                                                                         71.68 (6F, d, J = 715 Hz, PF.sub.6)                                                             107, 97 (24.69)                                                                           (2.06)                                                                            (5.76)                     5, 63  >300      -48.82 (1F, bs, NF)                                                                             278, 276                                                                              18.02                                                                             1.50                                                                              4.09                                        69.0-175.0 (6F, m, SbF.sub.6)                                                                   (M.sup.+ -3F)                                                                         (17.96)                                                                           (1.50)                                                                            (4.19)                     6        225-227.5                                                                             -48.75 (1F, bs, NF)                                                                             156, 155, 97,                                                                         30.50                                                                             2.23                                                                              7.12                              (with decompo.)             79      (30.38)                                                                           (2.53)                                                                            (7.09)                     9, 10, 29                                                                            99.5-110  -52.13 (1F, bs, NF)                                                                             299. 297                                                                              22.68                                                                             0.94                                                                              4.58                                        77.63 (3F, s, CF.sub.3)                                                                         295 (M.sup.+ -HF)                                                                     (22.80)                                                                           (0.96)                                                                            (4.43)                     11     120-125   -48.18 (1F, bs, NF)                                                                             177 (M.sup.+ -HF)                                                                     30.56                                                                             2.57                                                                              7.03                                        -38.21 (1F, s, S) 149     (30.46)                                                                           (2.56)                                                                            (7.10)                     12       135-136.5                                                                             -17.25 (bs, NF)   151, 139                                                                              58.00                                                                             7.05                                                                              3.74                                                                  (58.20)                                                                           (7.05)                                                                            (3.77)                     13, 64 162-164   -38.25 (1F, s, SO.sub.2 F)                                                                      237     39.36                                                                             4.52                                                                              5.90                              (decomposition)                                                                         -17.25 (1F, bs, NF)                                                                             219(M.sup.+ -HF)                                                                      (40.16)                                                                           (4.60)                                                                            (5.89)                     14       24-25.5 -17.63 (1F, bs, NF)                                                                             --      --  --  --                                          75.00 (3F, s, CF.sub.3)                                                                         --      --  --  --                         15, 17 168.5-170 -17.25 (1F, bs, NF)                                                                             139     37.15                                                                             3.87                                                                              4.66                                        77.62 (3F, s, CF.sub.3)                                                                         121     (37.37)                                                                           (3.84)                                                                            (4.84)                     16     126-128   -24.75 (1F, bs, NF)                                                                             255(M.sup.+ -HF)                                                                      34.86                                                                             3.26                                                                              5.03                                        77.75 (3F, s, CF.sub.3)   (34.91)                                                                           (3.30)                                                                            (5.09)                     18, 25, 34                                                                           140-143   -25.50 (1F, bs, NF)                                                                             227, 137, 69,                                                                         30.31                                                                             2.52                                                                              5.07                                        77.61 (3F, s, CF.sub.3)                                                                         59      (30.32)                                                                           (2.53)                                                                            (5.05)                     19     111-112   -48.37 (1F, bs, NF),                                                                            377(M.sup.+ -HF)                                                                      27.08                                                                             1.35                                                                              3.55                                        80.30 (3F, tt, J = 10.1, 3.0 Hz, CF.sub.3)                                                              (27.22)                                                                           (1.27)                                                                            (3.53)                                      114.2 (2F, m, CF.sub.2),                                                      120.9 (2F, m, CF.sub.2),                                                      125.2 (2F, M, CF.sub.2 S)                                    20     119.5-120.5                                                                             -37.13 (1F, bs, NF)                                                                             --      --  --  --                                          77.25 (3F, s, CF.sub.3)                                                                         --      --  --  --                         21     95-96     -0.75 (1F, bs, NF)                                                                              182, 179, 128                                                                         30.31                                                                             2.52                                                                              5.07                                        77.58 (3F, s, CF.sub.3)                                                                         113, 95, 69                                                                           (30.32)                                                                           (2.53)                                                                            (5.05)                     22       111-111.5                                                                             -0.75 (1F, bs, NF)                                                                              --      47.70                                                                             5.87                                                                              3.46                              (decomposition)                                                                         77.62 (3F, s, CF.sub.3)                                                                         --      (47.87)                                                                           (5.77)                                                                            (3.49)                     23     111.5-112.5                                                                             -51.00 (1F, bs, NF)                                                                             243, 187, 186                                                                         31.72                                                                             2.02                                                                              4.43                                        77.61 (3F, s, CF.sub.3)                                                                         137, 135, 113                                                                         (31.48)                                                                           (2.30)                                                                            (4.60)                     24     88- 91    -39.38 (1F, bs, NF)                                                                             --      --  --  --                                          77.63 (3F, s, CF.sub.3)                                                                         --      --  --  --                         26     79-80     -25.05 (1F, bs, NF)                                                                             163     --  --  --                                          77.98 (3F, s, CF.sub.3)                                                                         137     --  --  --                         28     55-58     -48.75 (1F, bs, NF) (*)                                                                         173 (M.sup.+ -HF)                                                                     --  --  --                         30     108-109   -50.59 (1F, bs, NF)                                                                             263, 261                                                                              26.38                                                                             1.53                                                                              5.81                                        70.70 (3F, s, CF.sub.3)                                                                         (M.sup.+ -HF)                                                                         (26.52)                                                                           (1.47)                                                                            (5.17)                     31, 33 105-108   -54.22 (1F, bs, NF)                                                                             341, 199                                                                              23.81                                                                             1.12                                                                              3.98                                        61.50 (3F, s, CF.sub.3)                                                                         197     (24.05)                                                                           (0.86)                                                                            (4.01)                                      78.10 (3F, s, CF.sub.3 S)                                    32     115-116   -50.02 (1F, bs, NF)                                                                             299 (M.sup.+ -HF)                                                                     33.74                                                                             2.73                                                                              4.28                                        77.68 (3F, s, CF.sub.3)   (33.86)                                                                           (2.85)                                                                            (4.39)                     35     57-65     -53.25 (1F, bs, NF)                                                                             --      --  --  --                                          77.61 (3F, s, CF.sub.3)                                                                         --      --  --  --                         36     110-115   -36.38 (1F, bs, NF)                                                                             --      --  --  --                                (decomposition)                                                                         77.61 (3F, s, CF.sub.3)                                                                         --      --  --  --                         37     112-116   -54.75 (1F, bs, NF)                                                                             --      --  --  --                                          77.61 (3F, s, CF.sub.3)                                                                         --      --  --  --                         38     115-116   -38.44 (1F, bs, NF)                                                                             137, 107, 79,                                                                         31.49                                                                             2.28                                                                              4.59                                        78.04 (3F, s, CF.sub.3)                                                                         78      (31.48)                                                                           (2.30)                                                                            (4.59)                     39     215-217   -17.25 (1F, bs, NF)                                                                             157, 139                                                                              42.37                                                                             4.75                                                                              6.24                                        149.6 (4F, s, BF.sub.4)   (42.33)                                                                           (4.88)                                                                            (6.17)                     40     84-88     -40.50 (1F, bs, NF)                                                                             241 (M.sup.+ -HF)                                                                     32.12                                                                             2.87                                                                              5.25                                        77.48 (3F, s, CF.sub.3)   (32.19)                                                                           (2.70)                                                                            (5.36)                     41     149.5-152 -19.75 (1F, bs, NF)                                                                             --      --  --  --                                          78.00 (3F, s, CF.sub.3)                                                                         --      --  --  --                         42     116-118   -40.05 (1F, bs, NF)                                                                             268 (M.sup.+ -HF)                                                                     39.29                                                                             4.22                                                                              4.50                                        78.02 (3F, s, CF.sub.3)                                                                         135, 120                                                                              (39.60)                                                                           (4.32)                                                                            (4.62)                     43     143-145   -39.99 (1F, bs, NF)                                                                             138, 110                                                                              44.21                                                                             5.32                                                                              5.64                                        150.6 (4F, s, BF.sub.4)   (44.85)                                                                           (5.44)                                                                            (5.81)                     44     112-114   -23.63 (1F, bs, NF)                                                                             210, 190                                                                              46.56                                                                             5.89                                                                              3.86                                        78.00 (3F, s, CF.sub.3)   (46.80)                                                                           (5.85)                                                                            (3.90)                     45     146-148   -40.00 (bs, NF)   120     --  --  --                         46     144-147   -51.88 (1F, bs, NF)                                                                             343 (M.sup.+ -HF),                                                                    32.84                                                                             2.46                                                                              3.84                                        78.00 (3F, s, CF.sub.3)                                                                         248, 182                                                                              (33.07)                                                                           (2.50)                                                                            (3.86)                     47     32        -27.38 (1F, bs, NF)                                                                             258     30.35                                                                             2.61                                                                              5.02                                        77.25 (3F, s, CF.sub.3)                                                                         257(M.sup.+ -HF),                                                                     (30.33)                                                                           (2.55)                                                                            (5.05)                                                        69                                         48     viscous   -50.10 (1F, bs, NF)                                                                             108     --  --  --                                          77.20 (1F, s, CF.sub.3)                                      49     151-152   -37.5 (1F, bs, NF)                                                                              --      --  --  --                                          77.30 (3F, s, CF.sub.3)                                      50     136-138   -28.88 (1F, bs, NF)                                                                             283 (M.sup.+ -HF)                                                                     39.84                                                                             4.36                                                                              4.41                                        78.00 (3F, s, CF.sub.3 )                                                                        135     (39.60)                                                                           (4.29)                                                                            (4.62)                     51       97-97.5 -27.00 (1F, bs, NF)                                                                             168, 167                                                                              51.83                                                                             6.95                                                                              3.33                                        77.62 (3F, s, CF.sub.3)                                                                         149     (52.05)                                                                           (6.99)                                                                            (3.37)                     52     131-133   -19.50 (1F, bs, NF)                                                                             249     53.72                                                                             3.19                                                                              3.42                                        77.25 (3F, s, CF.sub.3)                                                                         231     (54.10)                                                                           (3.26)                                                                            (3.51)                     53     238-239   -17.25 (1F, bs, NF)                                                                             266, 246                                                                              41.20                                                                             4.75                                                                              4.33                                        77.25 (3F, s, CF.sub.3)                                                                         232, 205                                                                              (41.38)                                                                           (4.70)                                                                            (4.39)                     54     162.5-163.5                                                                             -15.75 (1F, bs, NF)                                                                             139     35.07                                                                             3.26                                                                              4.43                                        77.72 (3F, s, CF.sub.3)                                                                         121     (35.18)                                                                           (3.26)                                                                            (4.56)                                      226.5 (1F, dt, J = 45, 10.5 Hz,                                               CH.sub.2 F)                                                  55     160-163   -14.63 (1F, bs, NF)                                                                             306, 305                                                                              32.65                                                                             2.70                                                                              4.14                                        77.62 (3F, bs, CF.sub.3)                                                                        157     (33.23)                                                                           (2.77)                                                                            (4.31)                                      228.0 (2F, dt, J = 45, 10.2 Hz,                                               CH.sub.2 F)                                                  56     193-195   -54.75 (1F, bs, NF)                                                                             375     24.9                                                                              0.85                                                                              3.64                                        61.50 (6F, s, β-CF.sub.3)                                                                  271     (25.08)                                                                           (0.79)                                                                            (3.66)                                      78.00 (3F, s, CF.sub.3)                                                                         69                                         57     94-96     -36.37 (1F, bs, NF)                                                                             361     43.63                                                                             2.72                                                                              3.58                                        77.40 (3F, s, CF.sub.3)                                                                         (M.sup.+ -HF)                                                                         (44.10)                                                                           (2.91)                                                                            (3.67)                     58     vsicous   -46.88 (1F, bs, NF)                                                                             241     31.17                                                                             2.72                                                                              5.26                                        78.00 (3F, s, CF.sub.3)                                                                         (M.sup.+ -HF)                                                                         (32.18)                                                                           (2.68)                                                                            (5.36)                     59     159       -15.75 (1F, bs, NF)                                                                             359     48.04                                                                             6.27                                                                              3.68                                        76.87 (3F, s, NF) 338     (47.75)                                                                           (6.14)                                                                            (3.71)                                                        190                                        60     162-168   -15.75 (1F, bs, NF)                                                                             306, 305                                                                              33.11                                                                             2.68                                                                              4.20                                        77.68 (3F, s, CF.sub.3)                                                                         175, 172                                                                              (33.23)                                                                           (2.77)                                                                            (4.31)                                      119.3 (2F, dd, J = 52.5, 10.6 Hz,                                                               157, 156                                                    CHF.sub.2)                                                   61, 62 90-91     -48.75 (1F, bs, NF)                                                                             104     32.53                                                                             2.64                                                                              7.43                                        149.6 (4F, s, BF.sub.4)   (32.43)                                                                           (2.70)                                                                            (7.57)                     65     208-209   -52.67 (1F, bs, NF)                                                                             169                                                                           167(M.sup.+ -HBF.sub.4)                                                               23.62                                                                             1.11                                                                              5.44                                        150.5 (4F, s, BF.sub.4)                                                                         165     (23.66)                                                                           (1.19)                                                                            (5.52)                     __________________________________________________________________________

The Following Examples 66-133 are contemplated to elucidate the use ofthe compounds according to the present invention as the fluorineintroducing agent.

EXAMPLE 66 ##STR127##

A methylene chloride solution (1 ml) containing 1.0 mmole of phenol and1.0 mmole of N-fluoro-3,5-dichloropyridinium trifluyoromethanesulfonatewas refluxed under an argon atmosphere for 5 hours. After the reactionwas completed, the reaction solution was analysed by gas chromatographyto reveal that it contained o-fluorophenol (0.44 mmole), p-fluorophenol(0.13 mmole), 2,4-difluorophenol (0.06 mmole), and phenol (0.27 mmole).Thus the yields of o-fluorophenol, p-fluorophenol and 2,4-difluorophenolwere 60%, 18%, and 7% respectively. The total yield was 88%corresponding to the total conversion of 73%. It is noted that nom-fluorophenol was formed.

EXAMPLE 67 ##STR128##

A 1,1,2-trichloroethane solution (2 ml) containing 1.0 mmole of phenoland 0.5 mmole of N-fluoropyriinium trifluoromethanesulfonate was heatedat 100° C. for 24 hours under an argon atmosphere and 0.25 mmole ofadditional N-fluoropyridinium trifluoromethanesulfonate, was added bothafter 3 hours and 6 hours, thus bringing the total amount ofN-fluoropyridinium trifluoromethanesulfonate to 1.0 mmole. After thereaction, the resulting reaction solution was subjected to gaschromatography to reveal that it contained 0.40 mmole of o-fluorophenol,0.14 mmole of p-fluorophenol, 0.05 mmole of 2,4-difluorophenol and 0.21mmole of phenol. Therefore, the yields of o-, p-fluorophenols and2,4-difluoro-phenol were 51%, 18% and 6% respectively, corresponding tothe total yields to 75%, with the total conversion of 79%.

EXAMPLES 68-133

A wide variety of fluorine- containing compounds were prepared byreacting N-fluoropyridinium salts according to the present inventionwith an equi-molar amount of compounds contemplated to be fluorinated.These examples were carried out similar to Example 66 with the reactionconditions set forth in Tables 7-10. The results obtained are alsoindicated in Tables 7-10. The identification of the structures of theresulting compounds were effected by comparing those with a standardspecimem or with spectroscopy.

In Tables 7-10, the N-fluoropydinium salts set foth below wereexpressed, for simplicity' sake, with the following No. of compounds:##STR129##

    TABLE 7        N-Fluoropyridinium     Fluorine  .sup.19 F-NMR (ppm) Example  salt     (indicated by  Temperature Hours Conversion containing Yield (CFCl.sub.3     internal No. Aromatic Compound compound number) Solvent (°C.) (b)     (%) compound (%) standard in CDCl.sub.3       68 phenol 3 CH.sub.2 CH.sub.2 room temp 18 78 o-fluorophenol 30 --        p-fluorophenol 24 --        2,4-difluorophenol  3 -- 69 phenol 4     CH.sub.2 CH.sub.2 reflux temp      5  o-fluorophenol 40 --        p-fluorophenol 11        2,4-difluorophen     ol  5 -- 70 phenol 5 CH.sub.2 ClCHCl.sub.2 100 16 80 o-fluorophenol 49     --        p-fluorophenol 14 --        2,4-difluorophenol trace -- 71     phenol 6 CH.sub.2 ClCHCl.sub.2 reflux temp 72 73 o-fluorophenol 24 -- 72     phenol 7 CH.sub.2 ClCHCl.sub. 2 100 24 75 o-fluorophenol 47 --     p-fluorophenol 31 --        2,4-difluorophenol  3 -- 73 phenol 14     CH.sub.2      Cl.sub.2 reflux temp 24 61 o-fluorophenol 84 --        p-fluorophenol     10 --        2,4-difluorophenol  1 -- 74 phenol 16 CH.sub.2 ClCHCl.sub.2     120 10 70 o-fluorophenol 45 --        p-fluorophenol 15 -- 75 phenol 17     CH.sub.2      ClCHCl.sub.2 120 10 70 o-fluorophenol 42 --        p-fluorophenol 15 --     76 anisole 2 CH.sub.2 ClCH.sub.2 Cl reflux temp 18 65 o-fluoroanisole 48     --        p-fluoroanisole 51 -- 77 anisole 1 CH.sub.2 ClCH.sub.2 Cl     reflux temp 18 58 o-fluoroanisole 40 --        p-fluoroanisole 47 -- 78     anisole 3 CH.sub.2 Cl.sub.2 reflux temp 24 71 o-fluoroanisole 44 --       p-fluoroanisole 48 --       79      2 CH.sub.2      Cl.sub.2 reflux temp 5 57     ##STR130##      71 140.3      80     ##STR131##      3 CH.sub.2      Cl.sub.2 reflux temp 3 79     ##STR132##      46 140.3      ##STR133##      23 149.6      81     ##STR134##      18 CH.sub.2      Cl.sub.2 reflux temp 50 85     ##STR135##      55 140.3      82     ##STR136##      2 CH.sub.2      Cl.sub.2 reflux temp 47 78     ##STR137##      51 140.3      83     ##STR138##      3 CH.sub.2      Cl.sub.2 reflux temp 25 62     ##STR139##      47 134.6      ##STR140##      31 149.6      84     ##STR141##      3 CH.sub.2      Cl.sub.2 reflux temp 48 53     ##STR142##      28 130.5      ##STR143##      24 117.8      85     ##STR144##      3 CH.sub.2      Cl.sub.2 reflux temp 32 68     ##STR145##      47 131.9      ##STR146##      32 119.1      ##STR147##      5 1158126.7      86     ##STR148##      2 CH.sub.2      Cl.sub.2 reflux temp 18 56     ##STR149##      71 133.1  87 p t butyphenol 2 CH.sub.2 Cl.sub.2 reflux temp 27 83     2-fluoro-4,1- 68 139.1        butylphenol        p-fluorophenol  7 123.5     88 2 naphthol 2 CH.sub.2 Cl.sub.2 room temp 26 80 1-fluoro-2- 84 155.2          naphthol      ##STR150##      11 101.6  89 benzene 3 benzene reflux temp 24 -- fluorobenzene 56 111.4              (in benzene solvent)

    TABLE 8        N-Fluoropyridinium    Fluorine  .sup.19 F-NMR (ppm) Example  salt     (indicated by  Temperature Hours Containing Yield (CFCl.sub.3 internal     No. Enol Compound compound number) Solvent (°C.) (h) compound (%)     standard in CDCl.sub.3)                90      ##STR151##      1 CH.sub.2      Cl.sub.2 room temp 7     ##STR152##      87 188(d, J=50Hz)      91     ##STR153##      7 CH.sub.2      Cl.sub.2 room temp 4     ##STR154##      57 188(d, J=50Hz)      92     ##STR155##      8 CH.sub.2      CH.sub.2 room temp 3     ##STR156##      65 188(d, J=50Hz)      93     ##STR157##      2 CH.sub.2      Cl.sub.2 room temp 2     ##STR158##      62 188(d, J=50Hz)      94     ##STR159##      6 CH.sub.2      Cl.sub.2 reflux temp 6     ##STR160##      41 188(d, J=50Hz)      95     ##STR161##      9 CH.sub.2      CH.sub.2 reflux temp 8     ##STR162##      23 188(d, J=50Hz)      96     ##STR163##      5 CH.sub.2      Cl.sub.2 room temp 5     ##STR164##      69 188(d, J=50Hz)      97     ##STR165##      10 CH.sub.2      Cl.sub.2 reflux temp 24     ##STR166##      40 188(d, J=50Hz)      98     ##STR167##      3 CH.sub.2      Cl.sub.2 reflux temp 3     ##STR168##      24 188(d, J=50Hz)      99     ##STR169##      1 CH.sub.2 Cl.sub.2 room temp 2 PhCHFCOOEt 65 180(d, J=48Hz)  100      ##STR170##      7 CH.sub.2 Cl.sub.2 room temp 2 PhCHFCOOEt 71 180(d, J=48Hz)  101      ##STR171##      7 CH.sub.2 Cl.sub.2 room temp 2 PhCHFCOOH 68 181(d, J=48Hz)  102      ##STR172##      11 CH.sub.2 Cl.sub.2 room temp 2 PhCHFCOOH 70 181(d, J=48Hz)  103      ##STR173##      1 CH.sub.2      Cl.sub.2 reflux temp 3     ##STR174##      58 188(m)      104     ##STR175##      1 CH.sub.2      Cl.sub.2 room temp 3     ##STR176##      31 168(t, J=51Hz)      ##STR177##      21 184(d, J=50Hz)      ##STR178##      10 206(d, J=50Hz)      105     ##STR179##      1 CH.sub.2      Cl.sub.2 room temp 1     ##STR180##      31 166(t, J=50Hz)      ##STR181##      11 183(d, J=50Hz)      ##STR182##      18 206(d, J=50Hz)      106     ##STR183##      1 CH.sub.2      Cl.sub.2 reflux temp 10     ##STR184##      48 166(t, J=48Hz)      ##STR185##      24 184(d, J=48Hz)      107     ##STR186##      1 CH.sub.2      Cl.sub.2 reflux temp 14     ##STR187##      31 166(t, J=49.5Hz)      ##STR188##      20 183(d, J=50Hz)      108     ##STR189##      1 CH.sub.2      Cl.sub.2 reflux temp 2     ##STR190##      59 192(m)      109     ##STR191##      15 CH.sub.2 CH.sub.2 CH.sub.3      CN(4/1) 15 1     ##STR192##      63 138(s)      110     ##STR193##      2 CH.sub.2      Cl.sub.2 reflux temp 24     ##STR194##      72 163(t, J=20Hz)      111     ##STR195##      7 CH.sub.2      Cl.sub.2 reflux temp 48     ##STR196##      83 163(t, J=20Hz)      112     ##STR197##      12 CH.sub.2      Cl.sub.2 reflux temp 48     ##STR198##      68 163(t, J=20Hz)      113     ##STR199##      2 CH.sub.2      Cl.sub.2 reflux temp. 15     ##STR200##      48 171(q, J=28Hz)      114     ##STR201##      1 CH.sub.2      Cl.sub.2 reflux temp 0.4     ##STR202##      59 177(m)     *the reaction product was hydrorized in a DMFconc. HCl aqueous soln (R1)

                                      TABLE 9                                     __________________________________________________________________________    Ex-                                                                           am-           N-Fluoropyndinium                                                                          Temper-                  .sup.19 F-NMR(ppm)        ple           salt (indicated by                                                                      Sol-                                                                             ature Hours                                                                             Fluorine containing                                                                      Yield                                                                             (CFCl.sub.3 internal      No.                                                                              Carbon anion                                                                             compound number)                                                                        vent                                                                             (°C.)                                                                        (h) compound   (%) standard in                                                                   CDCl.sub.3)               __________________________________________________________________________    115                                                                               ##STR203##                                                                              7         THF                                                                              room temp.                                                                          0.17                                                                               ##STR204##                                                                              78  162.8(t, J=20.3Hz)        116                                                                               ##STR205##                                                                              7         THF                                                                              room temp.                                                                          1                                                                                  ##STR206##                                                                              44  172.5(q, J=22.5Hz)        117                                                                               ##STR207##                                                                              7         THF                                                                              0     0.17                                                                               ##STR208##                                                                              78  158.0(q, J=21.9Hz)        118                                                                               ##STR209##                                                                              7         THF                                                                              0                                                                                        ##STR210##                                                                              42  144.6(q, J=48.6Hz)                                              ##STR211##                                                                               6  111.0(s)                  119                                                                               ##STR212##                                                                              7         THF                                                                              0- room temp.                                                                       0.17                                                                               ##STR213##                                                                              71  118.9(s)                  120                                                                              n-C.sub.12 H.sub.25 MgCl                                                                 7         Et.sub.2 O                                                                       0     0.5 n-C.sub.12 H.sub.25 F                                                                    75  210.8(tt, J=51.3,                                                             17Hz)                     121                                                                              PhMgCl     7         THF                                                                              0     0.17                                                                              PhF        58  --                        122                                                                               ##STR214##                                                                              7         THF                                                                              0     1                                                                                  ##STR215##                                                                              50  179.6(d,                  __________________________________________________________________________                                                        J=49.6Hz)             

    TABLE 10        N-Fluoropyridinium      F-NMR (ppm) Example  salt (indicated by     Temperature Hours  Yield (CFCl.sub.3 internal standard) No. Sulfide     compound number) Solvent (°C.) (h) α     fluorosulfide (%) Solvent 182.8(t, 52.5Hz)                 123      ##STR216##      7 CH.sub.2      Cl.sub.2 room temp. 8     ##STR217##      87 CDCl.sub.3 182.8(t, 52.5Hz)      124     ##STR218##      1 CH.sub.2      Cl.sub.2 room temp. 75     ##STR219##      48 CDCl.sub.3 182.8(t, 52.5Hz)  125 PhSCH.sub.3 7 CH.sub.2 Cl.sub.2     room temp. 4 PhSCH.sub.2 F 85 CDCl.sub.3 180.3(t, 54Hz)  126 PhSCH.sub.3     1 CH.sub.2 Cl.sub.2 room temp. 6 PhSCH.sub.2 F 56 CDCl.sub.3 180.3(t,     54Hz)  127 PhCH.sub.2 SCH.sub.3 7 CH.sub.2 Cl.sub.2 room temp. 1      ##STR220##      76 CH.sub.2 Cl.sub.2 CH.sub.2 Cl.sub.2 152.0(d, 56Hz)187.2(t, 51Hz)     128 PhCH.sub.2 SCH.sub.3 7 CH.sub.2      Cl.sub.2 0 3     ##STR221##      48 CH.sub.2 Cl.sub.2 CH.sub.2 Cl.sub.2 152.0(d, 56Hz)187.2(t, 51Hz)     129 n-C.sub.12 H.sub.25 SCH.sub.3 7 CH.sub.2 Cl.sub.2 room temp. 175     n-C.sub.12 H.sub.25 SCH.sub.2 F 41 CH.sub.2 Cl.sub.2 184.2(t, 52Hz)  130     CH.sub.3 SCH.sub.2 COOEt 7 CH.sub.2 Cl.sub.2 room temp. 10 CH.sub.1     SCHFCOOEt 48 CH.sub.2 Cl.sub.2 167.3(d, 54Hz)      131     ##STR222##      7 CH.sub.2      Cl.sub.2 room temp. 75     ##STR223##       40 CDCl.sub.2 183.8(t, 51Hz)      132     ##STR224##      13 CH.sub.2      Cl.sub.2 40 4.5     ##STR225##      75 CDCl.sub.3 182.8(t, 52.5Hz)  133 PhSC.sub.2 COOMe 7 CH.sub.2     Cl.sub.2 room temp. 23 PhSCHFCOOMe 45 CDCl.sub.3 158.4(d, 52Hz)

What is claimed is:
 1. A N-fluoropyridinium salt having the generalformula: ##STR226## wherein: (a) R¹ through R⁵ are each a group selectedfrom the class consisting of hydrogen, halogen, and methyl;(b) when atleast two of each of R¹ through R⁵ are hydrogen, then the remaining onethrough three groups of R¹ through R⁵ can each be selected from theclass consisting of:phenylcarbonyloxy substituted methyl, a mixture ofat least one fluoro substituted methyl group and at least one groupselected from the class consisting of methyl, trifluoromethyl andhalogen, and tertiary butyl or a mixture of methyl and t-butyl providedthat, when at least two of each of R¹ through R⁵ are tertiary butyl,said tertiary butyl groups are not adjacent; (c) when at least three ofeach of R¹ through R⁵ are hydrogen, then the remaining one or two groupsof R¹ through R⁵ can each be selected from the class consistingof:phenyl, acetyl, alkoxycarbonyl containing a total of 2 through 5carbon atoms wherein said aklyl substitute contains a total of 1 through4 carbon atoms, nitro cyano, alkoxy containing 1 through 10 carbonatoms, and acyloxy wherein said acyl group contains 1 through 4 carbonatoms; (d) when R³ is hydrogen, then R¹ and R² taken together and R⁴ andR⁵ taken together can each form a six-membered carbocyclic ring which isinclusive of two adjacent carbon atoms of the pyridine ring; .[.and.]..Iadd.or .Iaddend. (e) when R³ and R⁵ are each hydrogen, then R¹ and R²taken together can form a five-membered heterocyclic ring which containsone oxygen atom, which is inclusive of two carbon atoms of the pyridinering, and which has an oxo oxygen atom substituted on each ring carbonatom adjacent said ring oxy oxygen atom; and (f) X is a conjugate baseof a .[.Brosted.]. .Iadd.Bronsted .Iaddend.acid except for halides,.Iadd.provided that said N-fluoropyridinium salt is notN-fluoropyridinium hexafluoroantimonate, N-fluoropyridiniumhexafluoroarsenate, or N-fluoropyridinium hexafluoroiodate. .Iaddend. 2.The N-fluoropyridinium salt of claim 1 wherein X is selected from theclass consisiting of: --OSO₂ CF₃, --PF₆, .[.SbF₆, .]. --ClO₄, --OSO₂ F,--OSO₂ CH₃, ##STR227##
 3. A process for making an N-fluoropyridiniumsalt comprising reacting fluorine, a Bronsted acid containing aconjugate base except for haldies, and a pyridine compound in a reactionsolvent, said pyridine compound having a general formula: ##STR228##wherein: (a) R¹ through R⁵ are each a group selected from the classconsisting of hydrogen, halogen, and methyl;(b) when at least two ofeach of R¹ through R⁵ are hydrogen, then the remaining one through threegroups of R¹ through R⁵ can each be selected from the class consistingof:phenylcarbonyloxy substituted methyl, a mixture of at least onefluoro substitutedmethyl group and at least one group selected from theclass consisting of methyl, trifluoromethyl and halogen, and alkylcontaining two through four carbon atoms, provided that when each of twoof R¹ through R⁵ are tertiary butyl, said tertiary butyl groups are notadjacent; and (c) when at least three of R¹ through R⁵ are eachhydrogen, then the remaining one or two groups of R¹ through R⁵ can eachbe selected from the class consisting of:phenyl, acetyl, alkoxycarbonylcontaining a total of 2 through 4 carbon atoms wherein said alkylsubstitutent contains a total of 1 through 4 carbon atoms, nitro, cyano,alkoxy containing 1 through 10 carbon atoms, and acyloxy wherein saidacyl group contains 1 through 4 carbon atoms; (d) when R³ is hydrogen,then R¹ and R² taken together and R⁴ and R⁵ taken together can each forma six-membered carbocyclic ring which is inclusive of two adjacentcarbon atoms of the pyridine ring; .[.and.]. .Iadd.or .Iaddend. (e) whenR³ through R⁵ are each hydrogen, then R¹ and R² taken together can forma five-membered heterocyclic ring which contains one oxygen atom, whichis inclusive of two carbon atoms of the pyridine ring, and which has anoxo oxygen atom substituted on each ring carbon atom adjacent said ringoxy oxygen atom, .Iadd.provided that said conjugate base is not ⁻⁻ SbF₆,⁻⁻ AsF₆ , or ⁻⁻ IF₆, when R¹, R², R³, R⁴, and R⁵ are each hydrogen..Iaddend.
 4. The process of claim 3 wherein said reaction solvent isselected from the class consisting of acetonitrile, methylene chloride,chloroform, tri-chloromethane, trichlorofluoromethane,trichlorotrifluoromethane, ethyl acetate, diethyl ether, tetrahydrofuranand mixtures thereof at a temperature in the range of about -100° C. toabout 40° C., while maintaining the molar ratio of said Bronsted acid tosaid pyridine compound at least about 1:1, and wherein the molar ratioof said fluorine to said pyridine compound is at least about 1:1.
 5. Theprocess of claim 3 wherein said .[.Brosted.]. .Iadd.Bronsted.Iaddend.acid conjugate base is selected from the class consisting of:##STR229##